Utilization of greensand



Sept- 2, 1930. w. VAUGHAN Er AL UTILI ZATION OF GREENSAND Filed June s; 1927 Patented Sept.l 2,` 1930l l I Tiss4 'Illal'rlsoI STA PATN 'r vor-jlficl: j

.WILLIAM VAUGHAN, or MoUNTIIoLLY, NEW JERSEY, AND WILLIAM la.' Bauen, or

NEW YORK, N Y., ASS-IGNORS T0 THE PERMUTIT COMPANY, OF NEW YORK, N. Y.,

A. CORPORATION QF DELAWARE U'rILIzA'rIoN or GREESAND application areav vmme 3,1927. serial No. 196,2o2f1 This invent-ion relates to the utilization of greensa'nd; and it comprises a process where- 1n valuable materials are prepared from greensand or glauconite in an economical 5 manner by extracting linely divided greensand which is advantageously the fines resulting as a byproduct in obtaining granular glauconite with a hot mixture of -sulfurlc and hydrochloric acids to form a solution from which potash alum may be crystallized,

and a`resi^due which may be Washed to obtain silica freely soluble in alkali to make a solution of alkali silicate, the crystallization liquors and washing liquors being distilled to recover hydrochloric acid which may be returned to the system, leaving a residual liquor which may advantageously be employed in treatlng said granular greensand or Aglauconite to prepare it for water softening uses; all as more fully hereinafter set forth and as claimed.

Grreensand, or glauconite, is* a mineral found extensively throughout the United States, and particularly in New Jersey.l It

l5 occurs in theform of granules and is vprob-4 ably a complex salt, being a double silicate of'l iron and potassium, containing also :a large amount of alumina, with traces of other' basesysuch as lime and magnesia.- It has been 80 usedin a natural state as 'a fertilizer, and

many attempts lhave been made to extract the potash w ich imparts to the greensand its v value for' such purposes.

These attempts have not,"l however, met with commercial suc-y cess, as the cost of manufacture by the methods sov far proposed is in excess `of the normal-'sales value of the otash t'obe recovered. It hasv proved lmp'racticable to` produce'byproductsof commercial value to aid inmeeting the cost of manufacture.

Gluconite is possessed of water softening v properties and 1t now funda-wide industrial application for this purpose. For this urpose, lauconite is required in granular orm and es and underslzed granules are-not fused. The granules are treated in various ways prior touse. One such way involves treatments with sodium silicate vand acid-reacting chemicals, The glauconite is washed and afterwardstreated with a solution of al- "by arrows and circles. l

anules offgreensand kali or of an alkaline silicate, or both. This operation removes humus and certain other? impurities. As it is not desirable to leave the glauconite in an alkaline condition the treatment is usually followed/by one with a weak acid or an acid reacting chemical such as ferric sulfate, aluminum sulfate, etc. The use of these acid reacting salts is better than the use ofthe weak acids as involving less liability to loss of material. This method of preparing a base-exchange! water softening material entails the use of a plurality of solutions of chemicals, and the discarding of a high percentage of the greensand excavated.'

These features, of course, indicate increased 66 operating costs, with' resultant increase in thel cost of the finished water softening maf terial. f-

In the present invention,-we have developed a process by means of which the active 7o L fertilizing principle of greensand (potash) is recovered. in a commercially valuable form as p otash alum of high grade, practically free from iron, and wherein silica o'f high` acterized by treating the greensand with a mixture of sulfuric and hydrochloric acids',

with crystallization of alum from the extract and subsequentrecover of the hydrochloric acid, leaving a` residua solution which may so be utilizedin Ithe manufacture of water. soft- .ening materials in the above described process. The process may be a of greensand, but is partlcularly useful 1n lconnection with ythe fines above mentioned. 85`

While large or small maybe treated, we pregi to use the discard- .ed finesl from preparinlauconite for water softening purposes. is waste material .consists of greensand granules which will 100 grade is alsoprepared. The process is-char'- 75 pplied to any type I pass a 50 mesh sieve; granules larger than this being desired for water softening puroses. In the process illustrated in the flow sheet, the fines are subjected to a leaching or extracting treatment with a hot mixture of sulfuric and hydrochloric acids, which advantageously may be used in the ratios of 2 parts b'y volume of '20 per cent HCl and l first and allow some reaction and then add the sulfuric acid. Considerable heat is developed when the sulfuric acid joins the mixture of silica.

lauconite and acid and this heat is useful.

requently we run the surfuric acid into the mixture rather gradually, say, over a period of 2O to 3 0 minutes. This successive addition of acids has the advantage of minimizing escape of HC1 as gas from the hot system. The hot mixed acids and the glauconite are kept in contact sufficiently long to give a clean extraction; i. e., so that the undissolved silica is pure except for the trace of organic matter it ordinarily carries.' y

When the extraction is complete, the liquor br solution formed is drawn off or decanted, leaving a wet residue consisting essentially of somewhat porous silica wet with remaining acid liquid. The solution contains alum, iron sulfate,-`chlorides, etc. The residue is.

washed with-water, which may be cold or warm, the least quantity being used in order to conne the volume of the washings within reasonable limits. lThe washings are subsequently united with thesolution liquor, as described fully hereinafter.

The residue from Ithe washing treatment is a high grade silica, which may be marketed as such and used for making heat insulating bricks, filtering media, etc., but more -advantageousl it is dissolved in caustic soda solution to orm a 40 Baum solution of soldium silicate (waterglass). As stated, it may contain a little organic matter and if this ijs disadvantageous or its removal is Wanted, the silica may be first washed with a little dilute caustic soda solution which will remove'humus, etc., without much loss of We have found that the silica left after extraction, leaching-and washing is sufficiently soluble 'in alkali to make its use for this purpose highly advantageous. The solubility in alkali issuiiciently great to render Vpossible the manufacture of waterglass solutionscontaining a high ratio of silicato alkali. When the process of the present invention is performed in connection with the manufacture of water softening materialsl we convert the silica into waterglass solution and employ it in the manufacture of water softening materials, thereby reducing the manufacturing costs of both processes. (Circles 3 and 4.)

The solution resulting from the leaching operation indicated in the circle l of the flow sheet contains a mixture of iron, aluminum,

and potassium-salts, present in the form of potassium-aluminum sulfate, ferric and ferrous sulfates, ferrie and ferrous chlorids, etc. The solution is cooled, as indicated in circle 5, to effect the crystallization of potash alum or potassium-aluminum sulfate. The iron remains in solution in the mother liquor.

This mother liquor contains a further quantity of alum which is regained in a following operation. The crop of crystals so obtained is redissolved in water and again crystallized, to form a crop of purealum which may be marketed (circles 6 and 7).

'lhe hydrochloric acid employed in the primary leaching operation has an important function in the formation of pure alum. Not only does it facilitate a clean extraction, but it also converts the iron into chlorids which do not interfere with the crystalization of alum in a pure form.

According to the processthus far described, there have been prepared vin commercial form silica, sodium silicate, and-alum, as represented by circles 3, 4, 6 and 7. In 'a'fur'ther development of the process, the solutions and liquors resulting from such preparation are A collected and treated to regain further quantities of alum and to recover hydrochloric acid, which is returned for use in treating further quantities of greensand fines.

The washings obtained by purifying the silica (circle 8) may be concentrated if their volume be too great, and are added to the mother liquor obtained from the first crystallization of the alum crystals (circles 6 and 9). The united solutions, which contain practically all of the original hydrochloric acid used, together with some alum and practically all of the iron, are subjected to a distilling treatment to separate-the hydrochloric acid. This operation may be continued until all of the acid is removed, together with sufiicient water to form a 20 per cent solution, which is then returned to the leaching process (circle l0). It will be seen, therefore, that there is no substantial loss of hydrochloric acid, which circulates in the Is'stem in closed cycle. In distillingo the C1 and water the liquid is concentrated and on cooling it gives a further crop of alum crystals which are sent back to join the crude alum coming from the first crystallization. The mother liquor separated from this alum still contains some dissolved alum and it may contain in addition either aluminum sulfate or potassium sulfate as the case may be.

- 2q to return it for use in the described treat- Glauconite seldom contains alumina and potash in the exact ratio necessary `for alum and whichever is in excess occurs in this liquor as a sulfate. With potash in excess it is often economical to add some aluminum sulfate and regain it as alum. With aluminum sulfate in excess it is often economical to add kainite ,or other f cheap material containing KCl thereby incidentally replenishing the amount of HC1 in circulation. On .correcting the composition of the mother liquor and heating and cooling a further crop of alum crystals maybe obtained. The mother liquor contains a considerable amount of iron sul-- fate. [Sometimes it is worth while to utilize .this iron sulfate in the formation of 0pigmentar products. The -best use we have found or it however when the present invention `is practiced in connection with the manufacture of water softening .materials 1s ment of the granular glauconite. .It isan l. them for water softenin acid reacting liquid and can be used ef- 'ciently in treating glauconite granules. In

so doing'V the process becomes cyclic in the sense that glauconite is separated into granules and nes and the fines used-inpreparing reagents for treating the granules to adapt purposes.

It will be notedthat t e described process is a valuable auxiliary to a method of preparing glauconite for' water softening purposes since it enables use of the discarded fines for preparing the chemicals necessary in this method. The value ofthe chemicals which.

can be prepared aids in meeting the cost of the method. The only raw materials neces-- sary are sulfuric acid and causticqsoda with a slight amount of HC1 which may be re.- quir'ed for replenishment.A

In the extraction st a e while 'other pro-- j portions of I-ICl and 'HZS 4 may be employed,

we regard the proportions stated aslbeing the most practical.`

What we claim is l 1. In the 'utilization of greensand, the process which comprises subjectlng iinely d1- vided greensand to the. action of a hot solution containing a mixture of sulfuric and hydrochloric acids.v

`2. In the `utilization of greensand, the

process which comprises subjecting finely divided reensand to the action of a hot solu-I tion containing a 'mixture of sulfuric and .hy-

, drochloric acids, separating the resulting-solution-from the insoluble products formed by such action, and treating the resulting solution" to obtain hydrochloric .acid therefrom. Y

3. In the utilization of greensand,- the process whichcomprises subjecting finely divided greensand .tol the vaction'of a hot solution" containing' a i mixture of sulfuric 'and hydrochloricV acids, se aratingthe resultin ysolution from the inso uble .products form by such action, distilling 4hydrochloric acid from the resulting solution and returning the acid thusobtained to t e treatment of additional quantities of greensand.

4. In the utilization of greensand, the

process which comprises subjecting finely divided greensand to the action of asolution containing a mixture of sulfuric and hydrochloric acids, heating to facilitate extraction,` separating the residue from the resulting soj lution thus forme-d, Washing the residue to purifjt'the same,l adding the washings to the solution resulting from the acid treatment, and distilling the collected solutions to regain the hydrochloric acid.

5. In the utilization of greensand, the

process which comprises subjecting finely dithe residue to purify the same and thereby- ,obtain pure silica, cooling the resulting solution to effect the crystallization of alum therefrom,'uniting the washings obtained by l'purifying the residue with the mother liquor obtained by crystallizing the alum, distilling 'the collected body of liquor thus-obtained,

the'eby obtaining a solution of hydrochloric aci l v -7. In the utilization of glauconite, the process which comprises leaching glauconite with a solution of sulfuric and hydrochloric acids to give an alum-containing .solution and a residue of ure` silica and dissolving said silica 1n caustlc soda.

8. In'the utilization ofl glauconite, the process which comprises separating glauconite into granular materials and fines with subsequent treatment of the granules with silicate of soda andA acid-reacting materials, extracting the fines with a solution of sulfuric and hydrochloric acids toprepare a resulting solution containing alum and acid-reacting bodies and leave a residue of pure silica, dissolving the residue in caustic soda to form silicate of soda and employing the silicate Y for thetreatment of the granu s in the appropriate stage of operation and concentrating the liquid extract to' give crystals of alum and an acid mother liquor,.and returnin said mother liquor for use in treatment o the granules. 'f'

9. In theeconomic utilization `of glauco- Y nite the process which comprises separating natural glauconite into granular material and` fines, reserving the granular material for preparation of a Water softening material, extracting the fines with acid to obtain an acid reacting liquid, dissolving the residue from the acid extraction in caustic soda to form a sodium silicate solution and treating the granular material with an acid liquid and sodium silicate solution lderived from treatment of thefines in the described mannel. l

In Witness whereofy We have hereunto affixed our signatures.

WILLIAM VAUGI-IAN. WILLIAM M. BRUCE. 

